Crystal structure and spectral characteristics of {[(C6H5)NH]2C=NH(C6H5)}[B(C6H5)4]·C2H5OH

A novel compound of {[(C₆H₅)NH]₂C=NH(C₆H₅)}[B(C₆H₅)₄]·C₂H₅OH is prepared and examined by single crystal X-ray diffraction. Crystal data: C₄₅H₄₄BN₃O, M = 653.64, monoclinic, space group P2₁/c, unit cell parameters: a = 24.375(2) Å, b = 17.5829(15) Å, c = 18.090(1) Å, β = 105.277(2)°, V = 7479.0(11) ų, Z = 8, d _calc = 1.161 g/cm³, T = 293 K, R ₁ = 0.064. The structure contains two crystallographically independent cations, two anions, and two solvate ethanol molecules. Three types of interactions occur between them: interionic N-H(N)⋯π and N(H)⋯π⋯H(C), π-delocalized system of Ph rings of the anions, and interaction of ions with ethanol molecules N-H⋯O-H(O)⋯π. The compound is characterized by IR and luminescence spectra. At room temperature, the emission intensity grows with time of exposure to UV irradiation. Original Russian Text Copyright ? 2008 by T. M. Polyanskaya, E. A. Il’inchik, V. V. Volkov, M. K. Drozdova, O. P. Yur’eva, and G. V. Romanenko __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 3, pp. 512–521, May–June, 2008.     

Unsaturation in binuclear cyclopentadienylchromium carbonyl thiocarbonyls: Viability of (η-C5H5)2Cr2(CS)2(CO)3 in contrast to (η-C5H5)2Cr2(CO)5

The cyclopentadienylchromium carbonyl thiocarbonyls Cp₂Cr₂(CS)₂(CO)_n (n = 4, 3, 2, 1) have been studied by density functional theory using the B3LYP and BP86 functionals. The lowest energy Cp₂Cr₂(CS)₂(CO)₄ structure can be derived from the experimentally characterized unbridged Cp₂Cr₂(CO)₆ structure by replacing the two terminal carbonyl groups furthest from the Cr-Cr bond with two terminal CS groups. The two lowest energy Cp₂Cr₂(CS)₂(CO)₃ structures have a single four-electron donor η²-μ-CS group and a formal Cr-Cr single bond of length ∼3.1 Å. In contrast to the carbonyl analogue Cp₂Cr₂(CO)₅ these Cp₂Cr₂(CS)₂(CO)₃ structures are viable with respect to disproportionation into Cp₂Cr₂(CS)₂(CO)₄ and Cp₂Cr₂(CS)₂(CO)₂ and thus are promising synthetic targets. The lowest energy Cp₂Cr₂(CS)₂(CO)₂ structures have all two-electron donor CO and CS groups and short CrCr distances around ∼2.3 Å suggesting the formal triple bonds required to give the chromium atoms the favored 18-electron configurations. These Cp₂Cr₂(CS)₂(CO)₂ structures are closely related to the known structure for Cp₂Cr₂(CO)₄. In addition, several doubly bridged structures with four-electron donor η²-μ-CS bridges are found for Cp₂Cr₂(CS)₂(CO)₂ at higher energies. The global minimum Cp₂Cr₂(CS)₂(CO) structure is a triply bridged triplet with a CrCr triple bond (2.299 Å by BP86). A higher energy singlet Cp₂Cr₂(CS)₂(CO) structure has a shorter Cr-Cr distance of 2.197 Å (BP86) suggesting the formal quadruple bond required to give each chromium atom the favored 18-electron configuration.     

双核Fe配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2的合成和晶体结构

由侧链带有噻吩的环戊二烯基配体C5H5C6H10C4H3S与Fe(CO)5在二甲苯中加热回流,合成了1个新颖的四羰基二铁配合物[(η5-C5H4)C6H10(C4H3S)Fe(CO)2]2。通过元素分析、IR、1H NMR对其结构进行了表征,用X-射线单晶衍射确定了其结构。X-射线单晶衍射表明配合物中有2个桥羰基和2个端羰基,Fe-Fe的键长为0.25465(10)nm。     

Synthesis and crystal structure of (C3N5H6S)2[UO2(C2O4)2(H2O)] · C2N4H4

The formation of the thioammelinium cation in an aqueous solution in the presence of uranyl ions is demonstrated. Single crystal X-ray diffraction study of (C₃N₅H₆S)₂[UO₂(C₂O₄)₂(H₂O)] · C₂N₄H₄ was carried out and the geometric characteristics of thioammelinium were determined for the first time. The crystals are triclinc, space group , Z = 2, a = 8.5201(11) ?, b = 11.4027(14) ?, c = 14.329(2) ?, α = 103.182(5)°, β = 99.607(6)°, γ = 109.698(4)°, R = 0.0526. The main structural units in the crystal are mononuclear complex groups [UO₂(C₂O₄)₂(H₂O)]²⁻ corresponding to the crystal chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ²⁻ , M¹ = H₂O) of uranyl complexes. Uranium-containing mononuclear complexes are connected into a three-dimensional framework through electrostatic interactions and hydrogen bonds involving thioammelinium ions, water molecules, and cyanoguanidine. Original Russian Text ? L.B. Serezhkina, A.V. Virovets, E.V. Peresypkina, I.V. Medrish, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 5, pp. 380–385.     

Allyl complexes of molybdenum with Schiff base ligands. The crystal structures of [MoCl(CO)2{N(C6H4-2-OMe)C(Me)C5H4N}(η-C3H5)] and [MoCl(CO)2{N(Me)C(Ph)C5H4N}(η-C3H5)] are described

Treatment of the molybdenum tetracarbonyl complexes of [Mo(CO)₄L₂] (L₂=pyridyl amine Schiff base ligands) with allyl chloride in refluxing THF afforded η³-allyl complexes [MoCl(CO)₂L₂(η³-allyl)] (1-9). These complexes have been characterised by various techniques including ¹H-NMR, IR and FABMS spectroscopies and the single crystal X-ray structure determinations of the complexes [MoCl(CO)₂{N(C₆H₄-2-OMe)C(Me)C₅H₄N}(η³-C₃H₅)] (3) and [MoCl(CO)₂{N(Me)C(Ph)C₅H₄N}(η³-C₃H₅)] (4).     

Synthesis and crystal structures of [UO2(C6H4NO2)2(C6H5NO2)] and [UO2SO4(C6H5NO2)(H2O)] · H2O

The complexes [UO₂(C₆H₄NO₂)₂(C₆H₅NO₂) (I) and [UO₂SO₄(C₆H₅NO₂)(H₂O)] · H₂O (II) were synthesized and studied by X-ray diffraction analysis. Crystals I are monoclinic: a = 7.0081(3), b = 14.9624(7), c = 9.1837(5) ?, β = 96.594(2)°, Z = 2, space group P2₁/m. Crystals II are triclinic: a = 6.8097(6), b = 9.3837(8), c = 10.4556(10) ?, α = 85.279(3), β = 75.434(3), γ = 69.180(3)°, Z = 2, space group . The main structural unit of crystal I is a mononuclear fragment, which belongs to the crystal chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ are ions of pyridine-2-carboxylic (picolinic) acid, M¹ are molecules of picolinic acid) of the uranyl complexes. The main structural unit of crystal II is a chain, which belongs to the crystal chemical group AT³M ₂ ¹ (where T³-SO ₄ ²⁻ , M¹ are water and picolinic acid molecules) of the uranyl complexes. Picolinic acid in complexes I, II was found to have a zwitterion structure. Original Russian Text ? E.V. Grechishnikova, E.V. Peresypkina, A.V. Virovets, Yu.N. Mikhailov, L.B. Serezhkina, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 6, pp. 468–475.     

Cyclopentadienyl chromium and tungsten complexes with halide, methyl and σ-phenylethynyl ligands: Structures of (η-C5H5)Cr(NO)2(-CC-C6H5), (η-C5H5)Cr(NO)2I and [(η-C5H4)-COOCH3]W(CO)3Cl

With copper(I) iodide as catalyst, σ-alkynyls, compounds (η⁵-C₅H₅)Cr(NO)₂(CC-C₆H₅) (5), [(η⁵-C₅H₄)-COOCH₃]Cr(NO)₂(CC-C₆H₅) (10), and [(η⁵-C₅H₄)-COOCH₃]W(CO)₃(CC-C₆H₅) (13), were prepared from their corresponding metal chloride 1, 6 and 12. Structures of compound 3, 5 and 12 have been solved by X-ray diffraction studies. In the case of 5, there is an internal mirror plane passing through the phenylethynyl ligand and bisecting the Cp ring. The phenyl group is oriented perpendicularly to the Cp with an eclipsed conformation. The twist angle is 0° and 118.4° for -CC-Ph and two NO ligands, respectively. The orientation is rationalized in terms of orbital overlap between ψ₃ of Cp, dπ of Cr atom, and π^∗ of alkynyl ligand, and complemented by molecular orbital calculation. The opposite correlation was observed on the chemical shift assignments of C(2)-C(5) on Cp ring in compounds 6 and 12, using HetCOR NMR spectroscopy. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of ¹³C NMR data and compared with the calculations via density functional B3LYP correlation-exchange method.     

Synthesis and crystal structure of [Fe4O2(H2O)10(C5H5NCOO)4](NO3)8 · 2H2O

Crystals of the tetranuclear complex [Fe₄O₂(H₂O)₁₀(C₅H₅NCOO)₄](NO₃)₈ · 2H₂O are obtained by the slow evaporation of an aqueous solution of iron(III) nitrate and isonicotinic acid. According to the X-ray diffraction data, four metal atoms lie in the same plane and together with two μ₃-O oxygen atoms form the fragment [Fe₄(μ₃-O)₂]¹⁰⁺. The [Fe₄O₂(H₂O)₁₀(C₅H₅NCOO)₄]⁸⁺ cation has been obtained and structurally characterized for the first time.     

Synthesis, crystal structure and luminescence of a novel metal-organic polymer {Cd2(C4H2O4)2(C4H6N2)2(H2O)2 · 2H2O}n

The novel 3D coordination polymer {Cd₂(C₄H₂O₄)₂(C₄H₆N₂)₂(H₂O)₂ · 2H₂O} _n (I) has been synthesized and characterized by standard solid state methods including single-crystal X-ray crystallography. The compound crystallizes in triclinic space group P [`1]\bar 1 with a = 8.589(4), b = 10.585(3), c = 13.094(1) ?, α = 84.91(4)°, β = 79.21(0)°, γ = 83.76(4)°, V = 1159.5(1) ?³, Z = 2. The fumaric acid acts as a multimodal bridging ligand in the polymer unit. One of the fumaric acid ligands tridentately chelates to two Cd²⁺ cations in the same dinuclear unit, while the other bidentately chelates to two Cd²⁺ cations in another dinuclear unit. The two metal centers possess slightly distorted pentagonal bipyramid geometry with four Cd {(μ₄-fumarato)-(μ₂-fumarato)-bis(2-methylimidazolyl)-diaqua} units joining together to form a 28-membered ring. The whole molecule exhibits a through channel along y-axis and 2D layers in xz plane. With hydrogen bond and π-π interaction, the 2D layers construct a 3D microporous network.     

Derivatisation of boryl substituted titanium half-sandwich complexes - Molecular structures of [Ti{(η-C5H4)B(NiPr2)N(H)tBu}Cl2(NMe2)] and [{TiCl2(μ-{OB(NHMe2)-η-C5H4})}2-μ-O]

The half-sandwich complex [Ti{(η⁵-C₅H₄)B(NiPr₂)N(H)iPr}(NMe₂)₃] (6) was prepared from (η¹-C₅H₅)B(NiPr₂)N(H)iPr (5) and [Ti(NMe₂)₄] with cleavage of one equivalent of HNMe₂ and further converted into the corresponding constrained geometry complex [Ti{(η⁵-C₅H₄)B(NiPr₂)NiPr}(NMe₂)₂] (7) by elimination of a second equivalent of HNMe₂. Reaction of the half-sandwich complexes [Ti{(η⁵-C₅H₄)B(NiPr₂)N(H)R}(NMe₂)₃] (R = iPr, tBu) with excess Me₃SiCl yielded the corresponding dichloro complexes [Ti{(η⁵-C₅H₄)B(NiPr₂)N(H)R}Cl₂(NMe₂)] (R = tBu (10), iPr (11)). The intermediate species [Ti{(η⁵-C₅H₄)B(NiPr₂)N(H)iPr}Cl(NMe₂)₂] (9) could also be spectroscopically characterised. Partial hydrolysis of 10 and 11, respectively, resulted in formation of [{TiCl₂(μ-{OB(NHMe₂)-η⁵-C₅H₄})}₂-μ-O] (12). The molecular structures of 10 and 12 have been determined by X-ray crystallographic analyses. Complex 10, when activated with MAO, was found to be a highly active styrene polymerisation catalyst while being inactive towards the polymerisation of ethylene.     

夹心化合物Ni(C5H5)2的Xα研究

用Xα方法计算了Ni(C5H5)2的电子能级与归一化电荷,讨论了夹心化合物成键的特点,并用过渡态方法分析Ni(C5H5)2的光电子能谱及紫外可见吸收光谱,结果与实验相符。     

The preparation and crystal structure of (η-C5H5)(OC)3Mo(CH2)3C6H5

The reaction of with p-CH₃C₆H₄S(O)₂O(CH₂)₃C₆H₅ produces (η⁵-C₅H₅)(OC)₃Mo(CH₂)₃C₆H₅. This is only the second structurally characterized organometallic species in which an aromatic moiety is separated by three or more methylene groups. The alkyl chain adopts a staggered conformation, the Mo-C(1)-C(2)-C(3)-C(4) unit is nearly coplanar, and the alkyl chain eclipses the trans-carbonyl group on Mo. NMR evidence indicates that this conformation is preserved in solution.     

RE(C5H8NS2)3(C12H8N2)的标准摩尔生成焓

在无水乙醇中, 使低水合氯化稀土 (RE = Ho, Er, Tm, Yb, Lu) 与吡咯烷二硫代氨基甲酸铵 (APDC)和1,10-菲咯啉 (o–phen•H₂O) 反应, 制得其三元固态配合物. 用化学分析和元素分析确定它的组成为RE(C₅H₈NS₂)₃(C₁₂H₈N₂) (RE = Ho, Er, Tm, Yb, Lu). IR光谱说明RE³⁺ 分别与3个PDC^–的6个硫原子双齿配位, 同时与o–phen的2个氮原子双齿配位, 配位数为8. 用精密转动弹热量计测定了它们的恒容燃烧热△_cU分别为(-16788.46 ± 7.74), (-15434.53 ± 8.28), (-15287.80 ± 7.31), (-15200.50 ± 7.22)和(-15254.34 ± 6.61) kJ•mol^-1; 并计算了它们的标准摩尔燃烧焓△_cH_m^θ和标准摩尔生成焓△_fH_m^θ分别为( -16803.95 ± 7.74), (-15450.02 ± 8.28), (-15303.29 ± 9.28), (-15215.99 ± 7.22), (-15269.83 ± 6.61) kJ • mol^-1和 (-1115.42 ± 8.94), (-2477.80 ± 9.15), (-2619.95 ± 10.44), (-2670.17 ± 8.22), (-2650.06 ± 8.49) kJ•mol^-1.     

Synthesis, crystal structure, and biological activity of the binuclear complex [Pr2(C10H9N2O4)2(C7H5O3)4(H2O)2] · 2H2O

A novel binuclear praseodymium(III) complex with N-(2-propionyl)salicyloylhydrazone (C₁₀H₁₀N₂O₄, H₃L) and p-hydroxybenzoic acid (C₇H₆O₃, Phba) was prepared in a H₂O-C₂H₅OH mixed solution, and the crystal structure of [Pr₂(H₂L)₂(Phba)₄(H₂O)₂] · 2H₂O (I) was determined by X-ray single crystal diffractometry. Complex I crystallizes in the monoclinic system, space group P2₁/c, a = 1.1050(4), b = 1.9534(7), c = 1.2376(4) ?, β = 94.955(7)°, and Z = 4. In the structure each Pr³⁺ ion lies in a single capped square antiprism geometry coordinated by carboxyl O and acyl O atoms and azomethine N atom of one ligand (H₂L⁻ form), which coordinates via the keto form, four carboxyl O atoms from two Phba, and O atoms of two water molecules. In each molecule, two tridentate ligands were coordinated by the H₂L⁻ form, and each Pr³⁺ ion was chelated by the carboxyl group from Phba. The carboxyl groups of H₂L⁻ and other two Phba were coordinated via μ₂-bridging form and bidentate bridging form, respectively. Complex I and ligands Phba and H₃L were also searched for biological activity against Valsa mali by the growth rate method. The result showed that the inhibitory rate of ligands Phba and H₃L is better than complex I, especially Phba.     

Structure and luminescence of [Tb0.5(C6NO2H5)3(H2O)2]2n·(H3O)4n(ZnCl5)n(ZnCl4)2n

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb_0.5(C₆NO₂H₅)₃(H₂O)₂]_2n ·(H₃O)_4n (ZnCl₅) _n (ZnCl₄)_2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.     

配合物[Mn(C13H8N2OBr)2(C5H5N)2]·3C5H5N的结构与磁性研究

The complex [Mn(C₁₃H₈N₂OBr)₂(C₅H₅N)₂]·3C₅H₅N has been synthesized and characterized by X-Ray diffraction, IR and variable temperature (～10 to ～278K) magnetic susceptibility. X-Ray diffraction result for the single crystal shows that the crystal belongs to monoclinic, space group P2₁/c, a=1.0969(3)nm, b=2.0903(5)nm, c=2.0481(6)nm, β=97.366(6), V=4.657(2)nm³, Z=4, D_c=1.47g·cm^-3。     

Synthesis and X-ray structural characterization of mono(aminophosphine) derivatives of molybdenum hexacarbonyl, Mo(CO)5L {L?=?P(NC5H10)3, P(Ph)(NC4H8O)2 or P(Ph){N(i-C3H7)2}(NC4H8O)}

Equimolar reactions of molybdenum hexacarbonyl with tris(piperidino)phosphine (L1), bis(morpholino)(phenyl)phosphine (L2), and (Di-isopropylamino)(morpholino)(phenyl) phosphine (L3), which are examples of symmetrically and unsymmetrically substituted tertiary(amino)phosphines, afford the corresponding mono derivatives, Mo[P(NC₅H₁₀)₃)](CO)₅ (1), Mo[P(Ph)(NC₄H₈O)₂](CO)₅ (2), and Mo[P(Ph){N(i-C₃H₇)₂}(NC₄H₈O)](CO)₅ (3) in moderate yields as air stable crystalline solids. In the case of L1, some amount of trans-bis derivative, Mo[P(NC₅H₁₀)₃)]₂(CO)₄ (4), was also isolated. X-ray structures of 1, 2, and 3 have been determined. Compounds 1 and 2 crystallize in the monoclinic system with space group P21/c, while 3 crystallizes in the triclinic system with space group Pī. While the Mo-P and Mo-C_ax bond distances in these complexes are comparable with those of other P-C bonded phosphines, the presence of chiral phosphine seems to induce a relatively weaker interaction with the molybdenum center. Intermolecular hydrogen bonding is seen in compound 1.     

(Cyclopentadienyl){(N,N-dimethylaminoethyl)cyclopentadienyl} complexes of zirconium: Crystal structure of [(η-C5H5)(η-C5H4CH2CH2NHMe2)ZrCl2]2[ZrCl6]

[(η⁵-C₅H₅)ZrCl₃] reacts with [C₅H₄CH₂CH₂NMe₂]Li yielding the coordination polymer [(C₅H₅)(C₅H₄CH₂CH₂NMe₂)ZrCl₂]_n (1) as a brown solid which is very sensitive to moisture. The reaction of 1 with 1.35 equivalent of HCl (methanolic solution) yields pale yellow green crystals of [(η⁵-C₅H₅)(η⁵-C₅H₄CH₂CH₂NHMe₂)ZrCl₂]₂[ZrCl₆] (2). Compound 2 was fully characterized on the basis of NMR data and X-ray crystal structure analysis. The formation of this product indicates the elimination of C₅H₄CH₂CH₂NMe₂ as well as C₅H₅ ligands from the Zr(IV) metal centre.     

Dynamic behavior of [(η-C5H4CH3)Cr(CO)2(μ-SBu)Pt(PPh3)2] in solution

The structure and dynamic behavior of complex [(η⁵-C₅H₄CH₃)Cr(CO)₂(μ-SBu)Pt(PPh₃)₂] in solution was studied by multinuclear (¹H, ¹³C, ³¹P) NMR spectroscopy including a phase-sensitive NOESY experiment. Increasing temperature causes rupture of the Cr-Pt bond in the three-membered ring of the complex and rotation of the S-Pt(PPh₃)₂ unit around the Cr-S bond line, followed by formation of a new Cr-Pt bond to close the ring. All activation parameters for this dynamic process have been determined.